CN113113602B - Hard carbon negative electrode material for lithium ion secondary battery and preparation method thereof - Google Patents
Hard carbon negative electrode material for lithium ion secondary battery and preparation method thereof Download PDFInfo
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Abstract
The hard carbon negative electrode material is obtained by low-temperature acid washing and purifying a biomass raw material, has a pore structure, and has a total amount of magnetic substances lower than 5ppm and an oxygen content lower than 5%. The hard carbon negative electrode material for the lithium ion secondary battery and the preparation method thereof have the following beneficial effects: (1) The hard carbon negative electrode material prepared by the invention has a pore structure and higher specific capacity, and the first reversible capacity of the hard carbon negative electrode material is more than 420mAh/g. (2) The hard carbon cathode material prepared by the invention has low content of magnetic substances, is beneficial to improving the electrochemical performance, and can particularly improve the high-temperature storage performance of hard carbon used as the cathode material in a battery. (3) The hard carbon negative electrode material prepared by the method disclosed by the invention is low in oxygen content, the irreversible lithium ion loss can be reduced, the first efficiency is improved, and the first coulombic efficiency is more than 86%.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a hard carbon negative electrode material for a lithium ion secondary battery and a preparation method thereof.
Background
The lithium ion battery has the advantages of good stability, high energy density, no memory effect and the like, and is widely applied to the field of 3C consumer batteries, power batteries and energy storage batteries, the current commercial lithium ion battery negative electrode material mainly comprises a graphite negative electrode, but the theoretical specific capacity of the graphite negative electrode is lower and is only 372mAh/g, and the high-rate continuous charging and discharging capacity and the low-temperature performance are difficult to effectively improve, so that the development of a novel lithium ion battery negative electrode material which is high in specific capacity, excellent in rate performance and good in low-temperature performance is an important direction of current research.
Common hard carbon is hard graphitization carbon formed by thermally decomposing cross-linked resin with a special structure at about 1000 ℃, has high specific capacity and good cycle performance, and has large interlayer spacing, so that the hard carbon has excellent rate capability and low-temperature performance. When the hard carbon prepared by the conventional method is used as a negative electrode material, the charge-discharge voltage has large change along with the capacity, the charge-discharge curve is not smooth, the first coulombic efficiency is low, the irreversible lithium ion loss is large, the storage performance of the battery is obviously deteriorated, particularly the full-electricity storage performance of the battery in a high-temperature state, meanwhile, the currently reported preparation method of the hard carbon material is complex, the process is difficult to realize large-scale industrialization, the cost is high, and the large-scale commercial application of the hard carbon as the negative electrode material in the field of secondary batteries is limited due to the reasons.
Disclosure of Invention
In order to solve the problems, the invention provides a hard carbon negative electrode material for a lithium ion secondary battery, which is obtained by carrying out low-temperature acid washing and purification treatment on a biomass raw material, and has a pore structure, the total amount of magnetic substances of the hard carbon negative electrode material is lower than 5ppm, and the oxygen content of the hard carbon negative electrode material is lower than 5%.
Preferably, the biomass raw material comprises one or more of straw, sawdust, walnut shells, bagasse, rice chaff, wheat shells, coconut shells, apricot shells, peanut shells, wood, lignin and papermaking waste residues.
Preferably, the concentration of the acid in the low-temperature acid washing purification treatment is 5% -95%.
Preferably, the acid in the low-temperature acid washing purification treatment comprises one or more of carbonic acid, hydrofluoric acid, formic acid, acetic acid, stearic acid, hydrosulfuric acid, hypochlorous acid, oxalic acid, sulfurous acid, phosphoric acid, nitrous acid, perchloric acid, hydroiodic acid, sulfuric acid, hydrobromic acid, hydrochloric acid and nitric acid.
Preferably, the temperature of the solution in the low-temperature acid washing purification treatment is lower than 30 ℃.
Preferably, the hard carbon anode material has a porosity of 5% to 25%.
Preferably, the pore size of the hard carbon anode material is 0.05nm-40nm.
Preferably, the hard carbon negative electrode carbon material has a true density of 1.2g/cm3 to 1.7g/cm3.
Preferably, the hard carbon negative electrode carbon material has a specific surface area of 2g/m2 to 8g/m2.
The invention also provides a preparation method of the hard carbon negative electrode material for the lithium ion secondary battery, wherein the hard carbon negative electrode material comprises the hard carbon negative electrode material for the lithium ion secondary battery, and the method comprises the following steps:
calcining a biomass raw material with the average particle size of 1mm-5mm at the temperature of 200-500 ℃ to obtain a first calcined material;
crushing the first fired material to obtain a carbon precursor with the average particle size D50 of 10-20 mu m;
mixing the following components in percentage by mass (1-10): 20, adding the carbon precursor and the acid solution into a stirring tank with the temperature lower than 7 ℃ for stirring for 2-30 h, and controlling the temperature of the acid washing solution to be lower than 30 ℃;
arranging a screen mesh of 800-1000 meshes on a discharge hole of the stirring tank, and pouring the mixed solution;
adding deionized water into the stirring tank to repeatedly wash the mixed solution until the pH value of the mixed solution is 6-8;
removing the screen, and introducing the mixed solution into a spray dryer for solid-liquid separation to obtain dry powder;
calcining the dry powder at 1100-1300 ℃ for 2-8 h in an inert gas atmosphere to obtain a second calcined material, wherein the temperature rise speed is 1-5 ℃/min;
and carrying out jet milling, screening, demagnetizing and screening on the second sintered material to obtain the hard carbon cathode material.
The hard carbon negative electrode material for the lithium ion secondary battery and the preparation method thereof have the following beneficial effects:
(1) The hard carbon negative electrode material prepared by the invention has a pore structure and higher specific capacity, and the first reversible capacity of the hard carbon negative electrode material is more than 420mAh/g.
(2) The hard carbon cathode material prepared by the invention has low content of magnetic substances, is beneficial to improving the electrochemical performance, and can particularly improve the high-temperature storage performance of hard carbon used as the cathode material in a battery.
(3) The hard carbon cathode material prepared by the invention has low oxygen content, can reduce irreversible lithium ion loss and improve the first efficiency, and the first coulombic efficiency of the hard carbon cathode material is more than 86%.
(4) The carbon cathode material prepared by the invention has the advantages of low price of raw materials, mature preparation process and equipment and suitability for large-scale production.
(5) When the hard carbon negative electrode material prepared by the invention is used as a negative electrode active material of a lithium ion battery, the cycle performance of the battery can be obviously improved, and the capacity retention rate after 3900 cycles at the rate of 1C/1C is about 86%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an SEM image of a hard carbon anode material prepared in example 1 of the present invention;
fig. 2 is an XRD pattern of the hard carbon anode material prepared in example 1 of the present invention;
fig. 3 is a first charge-discharge curve of a button cell made of the hard carbon negative electrode material prepared in example 1 of the present invention;
fig. 4 is a cycle curve of the hard carbon anode material prepared in example 1 of the present invention at 1C/1C rate in a pouch cell.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
The invention provides a hard carbon negative electrode material for a lithium ion secondary battery, which is obtained by carrying out low-temperature acid washing and purification treatment on a biomass raw material, and has a pore structure, wherein the total amount of magnetic substances of the hard carbon negative electrode material is lower than 5ppm, and the oxygen content of the hard carbon negative electrode material is lower than 5%.
In an embodiment of the present application, the biomass raw material includes one or more of straw, sawdust, walnut shell, bagasse, rice chaff, wheat shell, coconut shell, apricot shell, peanut shell, wood, lignin and paper mill waste.
In the embodiment of the application, the concentration of the acid in the low-temperature acid washing purification treatment is 5-95%.
In the embodiment, the acid in the low-temperature acid washing purification treatment comprises one or more of carbonic acid, hydrofluoric acid, formic acid, acetic acid, stearic acid, hydrosulfuric acid, hypochlorous acid, oxalic acid, sulfurous acid, phosphoric acid, nitrous acid, perchloric acid, hydroiodic acid, sulfuric acid, hydrobromic acid, hydrochloric acid and nitric acid.
In the embodiment of the application, the temperature of the solution in the low-temperature acid washing purification treatment is lower than 30 ℃.
In the embodiment of the application, the porosity of the hard carbon negative electrode material is 5-25%.
In the embodiment of the application, the pore size of the hard carbon negative electrode material is 0.05nm-40nm.
In the examples of the present application, the true density of the hard carbon negative electrode carbon material is 1.2g/cm3 to 1.7g/cm3.
In the examples of the present application, the specific surface area of the hard carbon negative electrode carbon material is 2g/m2 to 8g/m2.
In an embodiment of the present application, the present invention also provides a method for preparing a hard carbon anode material for a lithium ion secondary battery, the hard carbon anode material comprising the hard carbon anode material for a lithium ion secondary battery as described in any one of the above, the method comprising the steps of:
calcining a biomass raw material with the average particle size of 1mm-5mm at the temperature of 200-500 ℃ to obtain a first calcined material;
crushing the first fired material to obtain a carbon precursor with the average particle size D50 of 10-20 mu m;
mixing the following components in percentage by mass (1-10): 20, adding the carbon precursor and the acid solution into a stirring tank with the temperature lower than 7 ℃ for stirring for 2-30 h, and controlling the temperature of the acid washing solution to be lower than 30 ℃;
arranging a screen mesh of 800-1000 meshes on a discharge hole of the stirring tank, and pouring the mixed solution;
adding deionized water into the stirring tank to repeatedly wash the mixed solution until the pH value of the mixed solution is 6-8;
removing the screen, and then introducing the mixed solution into a spray dryer for solid-liquid separation to obtain dry powder;
calcining the dry powder at 1100-1300 ℃ for 2-8 h under the inert gas atmosphere to obtain a second calcined material, wherein the temperature rise speed is 1-5 ℃/min;
and performing jet milling, screening, demagnetizing and screening on the second sintered material to obtain the hard carbon cathode material.
In the embodiment of the application, through analysis of an inductively coupled plasma emission spectrometer, the content of potassium in the hard carbon negative electrode carbon material is below 1ppm, the content of zinc is below 1ppm, the content of magnesium is below 1ppm, the content of iron is below 0.5ppm, and the total amount of magnetic substances is below 5 ppm.
In the embodiment of the application, the stirring tank is internally provided with a vertical baffle, so that the solution cannot form a vortex state in the stirring process; when the diameter of the stirring tank is below 1 meter, the number of the vertical baffles is 2, and when the diameter of the stirring tank is above 1 meter, the number of the vertical baffles is 4-6.
In the embodiment of the application, the jet mill used in the jet milling is one or more of a flat jet mill, a fluidized bed counter-jet type jet mill, a circulating tube type jet mill, a counter-jet type jet mill and a target type jet mill; the particle diameter D50 after jet milling is 3 μm to 15 μm, and more preferably 5 μm to 12 μm.
In the embodiment of the application, the rated magnetic field of the demagnetizer used in the demagnetization is more than or equal to 30000GS, and the background magnetic field is more than or equal to 8000GS.
In the embodiment of the application, the mesh number of the screen adopted in the screening is 325 meshes, and the particle size D100 of the screened material is less than or equal to 40 mu m.
Example 1
In the embodiment of the present application, a method for preparing a hard carbon negative electrode material for a lithium ion secondary battery provided by the present application specifically includes the following steps:
(1) Coarsely crushing coconut shells until the average particle size is about 1mm, then placing the coconut shells in a box-type furnace, introducing nitrogen for protection, heating to 500 ℃, and sintering for 2h. After natural cooling, crushing the sintering material to obtain a carbon precursor, wherein the particle size D50 of the carbon precursor is 11.6 microns;
(2) Adding diluted hydrochloric acid into a stirring tank of a high-speed dispersion machine, wherein the stirring tank is provided with a stainless steel sandwich wall, and ice water is introduced into the sandwich wall, and the temperature of the ice water is below 7 ℃. And (2) slowly adding the carbon precursor obtained in the step (1) into a stirring tank, wherein the mass ratio of the carbon precursor to the acid solution is 1: and 20, slowly stirring for 3 hours, and controlling the temperature of the pickling solution to be lower than 30 ℃.
(3) And (3) installing a double-layer screen mesh at the discharge port of the stirring tank, opening the discharge port, allowing the acid solution to flow out for repeated recycling, adding deionized water into the stirring tank, and repeatedly washing until the pH value is 6-8.
(4) And removing the screen, introducing the hard carbon precursor aqueous solution with neutral pH value into a spray dryer for solid-liquid separation to obtain dry powder, and sintering the dry powder at the high temperature of 1300 ℃ in the nitrogen atmosphere at the heating speed of 3 ℃/min for 2h to obtain a sintered material.
(5) And (3) performing jet milling on the sintered material obtained in the step (4) by a jet mill, wherein the particle size D50 after the jet milling is 3.2 mu m, screening by using a 325-mesh screen to remove large particles and foreign matters, demagnetizing and screening by using a 325-mesh screen again to obtain the hard carbon negative electrode material with uniform size, wherein the particle size D150 is 3.1 mu m, the true density is 1.28g/cm < 3 >, the specific surface area is 7.5g/m < 2 >, the oxygen content is 0.4% and the porosity is 11.3%.
Example 2
In an embodiment of the present application, a method for preparing a hard carbon negative electrode material for a lithium ion secondary battery provided by the present application specifically includes the following steps:
(1) Coarsely crushing apricot shells until the average particle size is about 2mm, then placing the apricot shells in a box type furnace, introducing nitrogen for protection, heating to 400 ℃, and sintering for 2 hours. After natural cooling, crushing the sintering material to obtain a carbon precursor, wherein the particle size D50 of the carbon precursor is 13.2 microns;
(2) Adding diluted hydrochloric acid into a stirring tank of a high-speed dispersion machine, wherein the stirring tank is provided with a stainless steel sandwich wall, and ice water is introduced into the sandwich wall, and the temperature of the ice water is below 7 ℃. And (2) slowly adding the carbon precursor obtained in the step (1) into a stirring tank, wherein the mass ratio of the carbon precursor to the acid solution is 1: and 17, slowly stirring for 10 hours, and controlling the temperature of the pickling solution to be lower than 30 ℃.
(3) And (3) installing a double-layer screen mesh at the discharge port of the stirring tank, opening the discharge port, allowing the acid solution to flow out for repeated recycling, adding deionized water into the stirring tank, and repeatedly washing until the pH value is 6-8.
(4) Removing the screen, introducing the hard carbon precursor aqueous solution with neutral pH value into a spray dryer for solid-liquid separation to obtain dry powder, and sintering the dry powder at 1250 ℃ in a nitrogen atmosphere at a high temperature of 3 ℃/min for 4h to obtain a sintered material.
(5) And (3) performing jet milling on the sintered material obtained in the step (4) by a jet mill, wherein the particle size D50 after the jet milling is 5.1 mu m, screening by using a 325-mesh screen to remove large particles and foreign matters, demagnetizing and screening by using a 325-mesh screen again to obtain the hard carbon negative electrode material with uniform size, wherein the particle size D150 is 4.9 mu m, the true density is 1.39g/cm < 3 >, the specific surface area is 5.4g/m < 2 >, the oxygen content is 1.3%, and the porosity is 6.0%.
Example 3
In the embodiment of the present application, a method for preparing a hard carbon negative electrode material for a lithium ion secondary battery provided by the present application specifically includes the following steps:
(1) Coarsely crushing the lignin until the average particle size is about 3mm, then placing the lignin in a box type furnace, introducing nitrogen for protection, heating to 300 ℃, and sintering for 2 hours. After natural cooling, crushing the sintered material to obtain a carbon precursor, wherein the particle size D50 of the carbon precursor is 16.7 microns;
(2) Adding diluted hydrochloric acid into a stirring tank of a high-speed dispersion machine, wherein the stirring tank is provided with a stainless steel sandwich wall, and ice water is introduced into the sandwich wall, and the temperature of the ice water is below 7 ℃. And (2) slowly adding the carbon precursor obtained in the step (1) into a stirring tank, wherein the mass ratio of the carbon precursor to the acid solution is 1: and 14, slowly stirring for 20 hours, and controlling the temperature of the pickling solution to be lower than 30 ℃.
(3) And (3) installing a double-layer screen on a discharge port of the stirring tank, opening the discharge port, allowing the acid solution to flow out for repeated recycling, adding deionized water into the stirring tank, and repeatedly washing until the pH value is 6-8.
(4) Removing the screen, introducing the hard carbon precursor aqueous solution with neutral pH value into a spray dryer for solid-liquid separation to obtain dry powder, and sintering the dry powder at a high temperature of 1200 ℃ in a nitrogen atmosphere at a heating rate of 3 ℃/min for 6h to obtain a sintered material.
(5) And (5) performing jet milling on the sintered material obtained in the step (4) by a jet mill, wherein the grain diameter D50 after the jet milling is 6.3 mu m, screening by using a 325-mesh screen to remove large grains and foreign matters, demagnetizing and screening by using a 325-mesh screen again to obtain the hard carbon negative electrode material with uniform size, wherein the grain diameter D50 is 6.2 mu m, the true density is 1.55g/cm < 3 >, the specific surface area is 3.9g/m < 2 >, the oxygen content is 2.7% and the porosity is 13.8%.
Example 4
In the embodiment of the present application, a method for preparing a hard carbon negative electrode material for a lithium ion secondary battery provided by the present application specifically includes the following steps:
(1) And coarsely crushing the papermaking waste residues until the average particle size is about 5mm, then placing the papermaking waste residues in a box type furnace, introducing nitrogen for protection, heating to 200 ℃, and sintering for 2 hours. After natural cooling, crushing the sintering material to obtain a carbon precursor, wherein the particle size D50 of the carbon precursor is 19.1 mu m;
(2) Adding diluted hydrochloric acid into a stirring tank of a high-speed dispersion machine, wherein the stirring tank is provided with a stainless steel sandwich wall, and ice water is introduced into the sandwich wall, and the temperature of the ice water is below 7 ℃. And (2) slowly adding the carbon precursor obtained in the step (1) into a stirring tank, wherein the mass ratio of the carbon precursor to the acid solution is 1: and 10, slowly stirring for 30 hours, and controlling the temperature of the pickling solution to be lower than 30 ℃.
(3) And (3) installing a double-layer screen mesh at the discharge port of the stirring tank, opening the discharge port, allowing the acid solution to flow out for repeated recycling, adding deionized water into the stirring tank, and repeatedly washing until the pH value is 6-8.
(4) Removing the screen, introducing the hard carbon precursor aqueous solution with neutral pH value into a spray dryer for solid-liquid separation to obtain dry powder, and sintering the dry powder at high temperature of 1100 ℃ in a nitrogen atmosphere at the heating speed of 3 ℃/min for 8h to obtain the sintered material.
(5) And (5) performing jet milling on the sintered material obtained in the step (4) by a jet mill, wherein the grain diameter D50 after the jet milling is 7.8 mu m, screening by using a 325-mesh screen to remove large grains and foreign matters, demagnetizing and screening by using a 325-mesh screen again to obtain the hard carbon negative electrode material with uniform size, wherein the grain diameter D50 is 7.5 mu m, the true density is 1.64g/cm < 3 >, the specific surface area is 2.1g/m < 2 >, the oxygen content is 4.8% and the porosity is 18.3%.
Comparative example 1
The difference from example 1 is that in step (1), the raw material is not coarsely crushed, and the rest is the same as example 1, and is not described herein again.
Comparative example 2
The difference from example 1 is that in step (2), the pickling process is not performed, and the rest is the same as example 1, and the description is omitted here.
Comparative example 3
The difference from example 1 is that in step (2), the temperature of the pickling solution is not controlled during the pickling process, and the rest is the same as example 1, and will not be described herein.
Comparative example 4
The difference from the embodiment 1 is that in the step (2), the stirring tank in the pickling process is not provided with a vertical baffle, and the rest is the same as the embodiment 1, and the description is omitted.
Comparative example 5
The difference from example 1 is that in step (4), the atomization drying technique is not used, but the ordinary stirring heating drying is used, and the rest is the same as example 1, and the description is omitted here.
Comparative example 6
The difference from example 1 is that step (5), i.e. jet milling, sieving, demagnetizing and sieving, is not performed, and the rest is the same as example 1, and will not be described again.
The carbon negative electrode materials in examples 1 to 4 and comparative examples 1 to 6 were tested by the following methods:
the range of material particle sizes was tested using a malvern laser particle sizer Mastersizer 3000.
The material was subjected to morphological analysis using a JSM-7160 scanning electron microscope from Japan Electron corporation.
The material is subjected to phase analysis by an XRD diffractometer (X' Pert3 Powder), and the grain size of the material is determined.
The material was tested for specific surface area using a conta NOVA 4000e usa.
The oxygen content in the material is accurately and rapidly determined by adopting an oxygen nitrogen hydrogen analyzer (ONH).
The powder true density was measured and calculated using an american mack true density instrument (AccuPyc II 1240D).
The specific surface area and porosity of the negative electrode material were determined using a U.S. Mach Chart and pore Analyzer (TriStar II 3020).
The contents of metallic elements and non-metallic elements were analyzed using an inductively coupled plasma emission spectrometer (ICP-OES) (Avio 200).
The hard carbon negative electrode materials obtained in the examples 1 to 4 and the comparative examples 1 to 6 are mixed in pure water according to a mass ratio of the hard carbon material, the conductive carbon black and the binder of 92. The button cells were assembled in a glove box filled with argon, the counter electrode was a metallic lithium sheet, the separator used was Celgard2400, and the electrolyte was 1mol/L EC/DMC of LiPF6 (Vol 1. And (3) performing charge and discharge tests on the button cell, wherein the voltage interval is 0.005V-1.5V, and the current density is 80mA/g. The first reversible capacity and efficiency of the carbon anode materials in examples and comparative examples were measured.
The hard carbon negative electrode material of example 1 was evaluated using a pouch full cell, wherein the positive electrode was a mature ternary positive electrode sheet, 1mol/L LiPF6/EC + DMC + EMC (v/v = 1) electrolyte, celgard2400 separator. On a LAND battery test system of Wuhanjinuo electronics Limited company, the electrochemical performance of the prepared soft package battery is tested, and the test conditions are as follows: and (3) charging and discharging at a constant current of 1.0 ℃ at normal temperature, wherein the charging and discharging voltage is limited to 2.75V-4.2V.
The testing equipment of the button cell and the soft package battery is a LAND battery testing system of Wuhanjinnuo electronic Co.
Performance test results of the hard carbon anode materials of examples 1 to 4 and comparative examples 1 to 6:
table 1 preparation process and composition of hard carbon anode materials in examples 1 to 4 and comparative examples 1 to 6:
table 2 electrochemical performance test data of the hard carbon anode materials in examples 1 to 4 and comparative examples 1 to 6:
as can be seen from table 1, the hard carbon negative electrode material prepared by the method of the present application has good electrochemical properties, and when used as a negative electrode active material of a lithium ion battery, it has excellent cycle performance.
In examples 1 to 4, the electrochemical performance of the hard carbon negative electrode material can be greatly influenced by changing the type of the hard carbon raw material, the particle size of the precursor, the acid washing condition, the sintering process, the jet milling particle size and the like. The hard carbon cathode material prepared by different raw materials has different internal structures and pores and different electrochemical performances. The size of the coarse particles can affect the uniformity of subsequent processes. The particle size of the precursor greatly influences the migration rate of lithium ions, and when the particle size is beyond the upper limit, the cycle performance of the precursor is slightly reduced. The acid washing process can enable the hard carbon negative electrode material to have a pore channel structure, increase lithium insertion sites, obviously improve the specific capacity of the hard carbon negative electrode material, reduce magnetic substances (mainly potassium, zinc, magnesium and iron elements) of the hard carbon negative electrode material and obviously improve the cycle performance.
In comparative example 1, the raw material is not coarsely crushed and is in a large block shape, or the particle size of the raw material is not controlled after coarse crushing, which causes non-uniformity of subsequent carbonization and acid washing purification processes, thereby causing poor material consistency, and the first reversible capacity and the first efficiency are reduced, and the cycle performance is greatly reduced.
In comparative example 2, the electrochemical performance of the composite negative electrode material is obviously affected by the inevitable high-content magnetic foreign matters in the hard carbon material without acid cleaning and purification, and the capacity retention rate of the soft package battery in 1C/1C cycle of 3900 weeks is only 64.5%.
In comparative example 3, the absence of control of the temperature of the pickling solution during the pickling process resulted in an increase in the oxygen content of the hard carbon material, thereby decreasing its reversible capacity, first efficiency and cycle performance.
In comparative example 4, the agitator tank in the pickling process was not equipped with a vertical baffle, which may result in insufficient pickling, poor material consistency, and decreased cycle performance.
In comparative example 5, the spray drying technique was not used, but the conventional stirring heating drying was used, which affected the morphology of the hard carbon negative electrode material and also increased the moisture content, thereby decreasing the reversible capacity and the cycle performance.
In comparative example 6, without jet milling, sieving, demagnetization, and sieving, the particle size D50 of the hard carbon material was significantly larger, reaching 20.8 μm, while the particle morphology and magnetic material were also poor, and the first efficiency and cycle performance were significantly deteriorated.
The hard carbon negative electrode material for the lithium ion secondary battery and the preparation method thereof have the following beneficial effects:
(1) The hard carbon negative electrode material prepared by the invention has a pore structure and higher specific capacity, and the first reversible capacity of the hard carbon negative electrode material is more than 420mAh/g.
(2) The hard carbon cathode material prepared by the invention has low content of magnetic substances, is beneficial to improving the electrochemical performance, and can particularly improve the high-temperature storage performance of hard carbon used as the cathode material in a battery.
(3) The hard carbon negative electrode material prepared by the method disclosed by the invention is low in oxygen content, the irreversible lithium ion loss can be reduced, the first efficiency is improved, and the first coulombic efficiency is more than 86%.
(4) The carbon cathode material prepared by the invention has the advantages of low price of raw materials, mature preparation process and equipment and suitability for large-scale production.
(5) When the hard carbon negative electrode material prepared by the invention is used as a negative electrode active material of a lithium ion battery, the cycle performance of the battery can be obviously improved, and the capacity retention rate after 3900 cycles at the rate of 1C/1C is about 86%.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (1)
1. A method for preparing a hard carbon anode material for a lithium ion secondary battery, the method comprising the steps of:
calcining a biomass raw material with the average particle size of 1mm-5mm at the temperature of 200-500 ℃ to obtain a first calcined material;
crushing the first fired material to obtain a carbon precursor with the average particle size D50 of 10-20 mu m;
mixing the following components in percentage by mass (1-10): 20, adding the carbon precursor and the acid pickling solution into a stirring tank with the temperature lower than 7 ℃ for stirring for 2-30 h, controlling the temperature of the acid pickling solution to be lower than 30 ℃, and arranging a vertical baffle in the stirring tank in the acid pickling treatment process;
arranging a screen mesh of 800-1000 meshes on a discharge hole of the stirring tank, and pouring the mixed solution;
adding deionized water into the stirring tank to repeatedly wash the mixed solution until the pH value of the mixed solution is 6-8;
removing the screen, and introducing the mixed solution into a spray dryer for solid-liquid separation to obtain dry powder;
calcining the dry powder at 1100-1300 ℃ for 2-8 h in an inert gas atmosphere to obtain a second calcined material, wherein the temperature rise speed is 1-5 ℃/min;
performing jet milling, screening, demagnetizing and screening on the second sintered material to obtain a hard carbon negative electrode material;
the hard carbon negative electrode material is obtained by performing low-temperature acid washing and purification treatment on a biomass raw material, has a pore structure, and has a total amount of magnetic substances lower than 5ppm and an oxygen content lower than 5%.
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| CN115020643A (en) * | 2021-09-09 | 2022-09-06 | 中南大学 | Biomass-based hard carbon, preparation method thereof and application thereof in sodium-ion battery |
| CN114927648B (en) * | 2022-05-06 | 2023-06-09 | 广东凯金新能源科技股份有限公司 | SnO-based 2 Artificial electrolyte interface film modified hard carbon negative electrode and preparation method thereof |
| CN115321516A (en) * | 2022-09-13 | 2022-11-11 | 惠州亿纬锂能股份有限公司 | Biomass-based hard carbon material, preparation method thereof and lithium ion battery |
| CN115403026A (en) * | 2022-09-13 | 2022-11-29 | 安徽清能碳再生科技有限公司 | Intelligent control system and method for preparing carbon-based material of negative electrode of energy storage battery |
| CN115991465B (en) * | 2022-11-22 | 2023-09-26 | 昆明理工大学 | Hard carbon material applied to sodium ion battery and preparation method thereof |
| CN116462176A (en) * | 2023-03-25 | 2023-07-21 | 温州大学碳中和技术创新研究院 | Ultra-fast preparation method of hard carbon negative electrode material of sodium ion battery |
| CN116553522A (en) * | 2023-06-16 | 2023-08-08 | 成都锂能科技有限公司 | Sodium ion negative electrode material with high specific surface area and preparation method thereof |
| CN116692829A (en) * | 2023-07-14 | 2023-09-05 | 河南省氟基新材料科技有限公司 | Preparation method and application of hard carbon anode material of sodium ion battery |
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